1. Field of the Invention
The present invention relates to a dye composition for keratinous fibers, which exhibits a stable and appropriate viscosity in a wide pH range and even in a system containing a salt or solvent at a high concentration, is excellent in usability and dyeing properties and is particularly suited for use with an acid dye.
2. Description of the Related Art
It is the common practice to incorporate, in a dye composition for keratinous fibers such as hair dye, a thickener with a view toward preventing liquid dripping, thereby improving handling use of it or improving retention of the dye in keratinous fibers. As such a thickener, natural polymers such as xanthan gum and guar gum, and semi-synthetic polymers such as methyl cellulose and hydroxyethyl cellulose are employed by way of example.
In a dye composition, an acid dye, basic dye, oxidation dye or the like is contained as a dye. Suitable pH conditions are necessary for effective staining of keratinous fibers with this dye. For example, keratinous fibers are dyed well with an acid dye at a pH in the vicinity of 1.5 to 5, and with an oxidation dye at a pH in the vicinity of 6 to 10. Thus, it is necessary to adjust the pH to fall within a wide range, depending on the kind of a dye.
In general, however, a thickener exhibits good thickening effects within a limited pH range and many thickeners lack in stability at a low pH. Xanthan gum or the like is known as a thickener rather free from the influence of pH. Xanthan gum was however accompanied with the problems that owing to insufficient fluidity of a dye composition containing it, the composition dripped as a mass when applied to the hair by hands or some tool. In addition, the dye composition containing xanthan gum involved problems in usability, that is, low spreadability over the hair and in dyeing properties. Thus, a dye composition containing an acid dye conventionally used within a particularly low pH range was not sufficient in usability and dyeing properties.
An object of the present invention is therefore to provide a dye composition for keratinous fibers which composition exhibits a stable and appropriate viscosity in a wide pH range and even in a system containing a salt or solvent at a high concentration, and is excellent in usability and dyeing properties.
The present inventors have found that a dye composition for keratinous fibers which can satisfy the above-described object is available by incorporating therein a specific anionic partially crosslinked polymer.
In the present invention, there is thus provided a dye composition for keratinous fibers, which comprises the following components (A) and (B):
(A) a hydrolyzate of a lower alkyl vinyl ether/maleic anhydride copolymer partially crosslinked with a terminally unsaturated diene compound, or a monoalkyl ester of the hydrolyzate; and
(B) a dye.
The dye composition for keratinous fibers according to the present invention has a stable and appropriate viscosity in a wide pH range and even in a system containing a salt or solvent at a high concentration; and has excellent usability and dyeing properties. It is particularly suited for use with an acid dye.
The lower alkyl vinyl ether/maleic anhydride copolymer partially crosslinked by a terminally unsaturated diene compound (which copolymer will hereinafter be called xe2x80x9cpartially crosslinked polymerxe2x80x9d, simply), one of the components to be used in the present invention, is as described in U.S. Pat. No. 5,539,039 and U.S. Pat. No. 5,874,510. By the hydrolysis of it, the hetero ring of maleic anhydride becomes a dicarboxylic acid, whereby a colorless transparent gel is formed.
Examples of the lower alkyl group of the lower alkyl vinyl ether to be used for the partially crosslinked polymer include C1-4 alkyl groups. Among them, methyl and ethyl groups are preferred, with methyl group being particularly preferred.
The molar ratio of the lower alkyl vinyl ether to maleic anhydride in the partially crosslinked polymer ranges from 40:60 to 60:40, with a range of from 45:55 to 55:45 being particularly preferred.
Examples of the terminally unsaturated diene compound to be used as a crosslinking agent include C6-18 compounds such as 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, 1,15-hexadecadiene, divinylbenzene, ethylene dimethacrylate, methacrylic anhydride and diaryl phthalate. Among them, terminally unsaturated alkadienes are preferred, with 1,9-decadiene being particularly preferred.
The crosslinking degree of the partially crosslinked polymer by the above-described crosslinking agent is preferred to be 1 to 5%, especially 2 to 4% and its average molecular weight is preferably at least 1000,000.
Such a partially crosslinked polymer is available as a uniform suspension by polymerizing a lower alkyl vinyl ether and maleic anhydride in a proper solvent in the presence of a crosslinking agent (a terminal unsaturated diene compound) and a polymerization initiator at 60 to 80xc2x0 C. As the solvent and polymerization initiator, isopropyl acetate an the like, and 2,2xe2x80x2-azobis (2-methylbutanenitrile), decanoyl peroxide and the like can be used, respectively.
As the partially crosslinked polymer, commercially available products can also be employed. Examples include xe2x80x9cStabileze 06xe2x80x9d and xe2x80x9cStabileze QMxe2x80x9d (each, trade name; product of ISP Inc.), that is, a methyl vinyl ether/maleic anhydride copolymer partially crosslinked with 1,9-decadiene.
As described above, by the hydrolysis to convert the hetero ring of maleic anhydride into a dicarboxylic acid, the partially crosslinked polymer forms a colorless transparent gel. This hydrolysis is effected in a manner known per se in the art, for example, by dispersing the polymer in water and then heating. The partially crosslinked polymer wherein the dicarboxylic acid has partially been monoalkyl esterified is also usable and in this case, C1-4 alkyl groups are preferred as the alkyl group. Esterification can be conducted, for example, by reacting the partially crosslinked polymer with a lower alcohol corresponding to the alkyl group in a solvent such as acetone. A desired viscosity is available by neutralizing the hydrolyzate or monoalkyl ester thereof with an alkali as needed.
Examples of the alkali usable for neutralization include inorganic alkali agents such as sodium hydroxide and potassium hydroxide; organic alkali agents such as monoethanolamine, diethanolamine, triethanolamine and aminopropanol; ammonia: carbonates such as ammonium carbonate, potassium carbonate, sodium carbonate and guanidine carbonate; basic amino acids such as arginine. Among them, alkali metal hydroxides are preferred.
The content of Component (A) in the dye composition for keratinous fibers according to the present invention is preferably 0.1 to 15 wt. %, with 0.5 to 10 wt. % being particularly preferred.
As the dye [Component (B)] to be used in the present invention, preferred are acid dyes, basic dyes, nonionic dyes and oxidation dyes, with acid dyes being particularly preferred.
Examples of the acid dye include Acid Red 27 (C.I. 16185), Acid Red 51 (C.I.45430), Acid Red 18 (C.I. 16255), Acid Red 92 (C.I. 45410), Acid Red 94 (C.I. 45440), Acid Red 52 (C.I. 45100), Acid Yellow 23 (C.I. 19140), Food Yellow 3 (C.I. 15985), Food Green 3 (C.I. 42053), Food Blue 2 (C.I. 42090), Acid Blue 74 (C.I. 73015), Pigment Red 57-1 (C.I. 15850), Acid Red 33 (C.I. 17200), Acid Red 87(1) (C.I. 45380), Acid Red 92 (C.I. 45410), Acid Red 94 (C.I. 45440), Acid Orange 7 (C.I. 15510), Acid Red 95 (C.I. 45425), Acid Yellow 73 (C.I. 45350), Acid Yellow 3 (C.I. 47005), Acid Green 25 (C.I. 61570), Acid Green 5 (C.I. 42095), Acid Blue 5 (C.I. 42052), Acid Blue 9 (C.I. 42090), Acid Orange 24 (C.I. 20170), Acid Violet 9 (C.I. 45190), Food Red 6 (C.I. 16155), Acid Red 26 (C.I. 16150), Food Red 1 (C.I. 14700), Acid Red 88 (C.I. 15620), Acid Orange 20 (C.I. 14600), Acid Yellow 40 (C.I. 18950), Acid Yellow 1 (C.I. 10316), Acid Yellow 36 (C.I. 13065), Acid Yellow 11 (C.I. 18820), Acid Green 1 (C.I. 10020), Acid Green 3 (C.I. 42085), Acid Violet 43 (C.I. 60730), Acid Black 1 (C.I. 20470), Acid Black 52 (C.I. 15711), Acid Blue 1 (C.I. 42045), Acid Blue 3 (C.I. 42051), Acid Blue 62 (C.I. 62045), Acid Brown 13 (C.I. 10410), Acid Green 50 (C.I. 44090), Acid Orange 3 (C.I. 10385), Acid Orange 6 (C.I. 14270), Acid Red 14 (C.I. 14720), Acid Red 35 (C.I. 18065), Acid Red 73 (C.I. 27290), Acid Red 184 (C.I. 15685) and Brilliant Black 1 (C.I. 28440).
Examples of the basic dye include Basic Blue 7 (C.I. 42595), Basic Blue 26 (C.I.44045), Basic Blue 99 (C.I. 56059), Basic Violet 10 (C.I. 45170), Basic Violet 14 (C.I. 42515), Basic Brown 16 (C.I. 12250), Basic Brown 17 (C.I. 12251), Basic Red 2 (C.I. 50240), Basic Red 22 (C.I. 11055), Basic Red 76 (C.I. 12245), Basic Red 118 (C.I. 12251:1), Basic Yellow 57 (C.I. 12719), basic dyes, as described in Japanese Patent Publication No. 2204/1983 and Japanese Patent Application Laid-Open No. 118832/1997, which contain, at the side chain of the aromatic ring thereof, a quaternized nitrogen atom, and basic dyes, as described in Japanese-Language Laid-Open Publication (PCT) No. 502946/1998 and Japanese Patent Application Laid-Open No. 182379/1998, which are represented by the below-described formula and contain a quaternized nitrogen atom which may be non-localized and a xe2x80x94Zxe2x95x90Nxe2x80x94 bond (Z represents a nitrogen atom or a group xe2x80x94CHxe2x95x90).
Examples of the nonionic dyes include so called nitro dyes, such as those as described in U.S. Pat. No. 4,834,768, from line 65 of the second column to line 31 of the third column. 
It is preferred to incorporate the above-exemplified acid dye or basic dye to the dye composition of the present invention in an amount of 0.01 to 10 wt. %, more preferably 0.01 to 5 wt. %, especially 0.05 to 3 wt. % based on the whole composition.
Addition of a solvent as a penetration promoter is preferred when an acid dye or basic dye is employed. Examples of such a solvent include C1-6-alkyl-containing monohydric alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol; C6-6 alcohols having at least two hydroxyl groups or ethers thereof such as propanediol, butanediol, pentanediol, hexanediol, hexanetriol, heptanediol, heptanetriol, octanediol, octanetriol, isopreneglycol, propyleneglycol, glycerin, diethylene glycol monoethyl ether, diethylene glycol diethyl ether and ethylene glycol monoethyl ether; N-alkylpyrrolidones which are liquid at normal temperature such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone; lower alkylene carbonates such as ethylene carbonate and propylene carbonate; and aromatic alcohols such as benzyl alcohol, benzyloxy ethanol, cinnamyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, phenoxy isopropanol, 2-benzylethanol and xcex2-phenylethyl alcohol. Among them, aromatic alcohols, lower alkylene carbonates, N-alkyl pyrrolidones are preferred, with benzyl alcohol, benzyloxy ethanol and propylene carbonate being particularly preferred. These solvents may be used either singly or in combination. The solvent is preferably added in an amount of 0.1 to 60 wt. % to the dye composition of the present invention.
When an oxidation dye is employed, an intermediate for the oxidation dye can be used in combination for the formulation of a first hair dye component. As the intermediate for the oxidation dye, a developer and coupler are employed.
Examples of the developer include xe2x80x94NH2xe2x80x94, xe2x80x94NHRxe2x80x94 or xe2x80x94NR2-containing p-phenylenediamines (R represents a C1-4 alkyl or hydroxyalkyl group) such as p-phenylenediamine, p-toluylenediamine, N-methyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-2-methyl-p-phenylendiamine, N-ethyl-N-(hydroxyethyl)-p-phenylenediamine, chloro-p-phenylenediamine, 2-(2xe2x80x2-hydroxyethylamino)-5-aminotoluene, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, methoxy-p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-bromo-p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 6-methoxy-3-methyl-p-phenylenediamine, 2,5-diaminoanisole, N-(2-hydroxy-propyl)-p-phenylenediamine and N-2-methoxyethyl-p-phenylenediamine; 2,5-diaminopyridine derivatives; and p-aminophenols, o-aminophenols and o-phenylenediamines such as p-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2,4-diaminophenol and 5-aminosalicylic acid.
Examples of the coupler include xcex1-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, benzcatechin, pyrogallol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, 5-(2xe2x80x2-hydroxyethylamino)-4-methoxyphenol, hydroquinone, 2,4-diaminoanisole, m-toluylenediamine, 4-aminophenol, resorcin, resorcin monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-amino-5-pyrazolone, 1-phenyl-3,5-diketopyrazolidine, 1-methyl-7-dimethylamino-4-hydroxy-2-quinolone, m-aminophenol, 4-chlororesorcinol, 2-methylresorcinol, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 3,5-diaminotrifluoromethylbenzene, 2,4-diaminofluorobenzene, 3,5-diaminofluorobenzene, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-triaminopyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine and 4,6-diamino-2-hydroxypyrimidine.
As the developer or coupler, at least one of the above-exemplified ones may be used. It is preferably added in an amount of 0.01 to 20 wt. %, especially 0.5 to 10 wt. % based on the whole composition.
As the pH of the dye composition of the present invention, preferred is 1.5 to 5, especially 2 to 4 and more preferably 2.5 to 4 when an acid dye is employed as a dye; preferred is 5 to 14, especially 8 to 10 when a basic dye is employed; or preferred is 6 to 14, especially 8 to 10 when an oxidation dye is employed. This pH value is that of the stock solution of the dye composition measured without dilution. The dye composition of the present invention has a viscosity appropriate for dyeing operation and exhibits excellent dyeing properties even within the above-described pH range.
Examples of an acid to be used for pH adjustment include organic acids and salts thereof such as succinic acid, malonic acid, maleic acid, fumaric acid, citric acid, maleic acid, acetic acid, lactic acid, oxalic acid, tartaric acid, formic acid, glycolic acid, levulinic acid and isethionic acid and salts thereof; and inorganic acid such as phosphoric acid and hydrochloric acid. Among them, citric acid, lactic acid, glycolic acid and levulinic acid are preferred. Examples of the alkali agent include inorganic alkali agents such as sodium hydroxide and potassium hydroxide; organic alkali agents such as monoethanolamine, diethanolamine, triethanolamine and aminopropanol; ammonia; ammonium chloride; carbonates such as ammonium carbonate, potassium carbonate, sodium carbonate and guanidine carbonate; and basic amino acids such as arginine. Among them, alkali metal hydroxides are preferred.
To the dye composition of the present invention, a thickener other than Component (A) can be added. Examples of such a thickener include carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, gum arabic, carrageenan, Karaya gum, tragacanth gum, wellan gum, carob gum, Gum Quince seed (quince), casein, dextrin, gelatin, sodium pectate, sodium alginate, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, sodium polyacrylate, polyacrylic amide, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, aluminum magnesium silicate and bentonite.
In addition to the above-described components, components ordinarily employed for cosmetics can be incorporated in the dye composition of the present invention as needed. Examples include surfactants, cationic polymers, lower alcohols, polyols, oil components, silicone derivatives, pigments, chelating agents, perfumes, antiseptics, ultraviolet absorbers, antioxidants, bactericides and propellants. The dye composition of the present invention can be prepared in a conventional manner. The dye composition of the present invention can be prepared in any form such as transparent liquid, emulsion, cream, gel, paste or mousse.
As the keratinous fibers to which the dye composition of the present invention is applied, hair is preferred.